Normally crystalline vinylidene chloride polymer latex and fiber modified cement compositions having enhanced elastic modulus

ABSTRACT

Normally crystalline vinylidene chloride polymer latex-modified portland cement compositions having exceptionally high elastic modulus by the incorporation therein of from about 1.5 to about 3 percent of composition volume of a fibrous mixture consisting of (a) a nylon fiber and (b) a steel fiber wherein the fibrous materials are present in the mixture in amounts representing a ratio of (a) to (b) of about 1:2 to 2:1 based on mixture volume; which compositions are particularly suited for use in construction in preparing or repairing structures such as pavement and the like requiring high energy absorption properties.

United States Patent Eash et a1. Nov. 20, 1973 [5 NORMALLY CRYSTALLINE VINYLIDENE 2,819,239 1/1958 Eberhard et a1 260/29.6 S CHLORIDE POLYMER LATEX AND FIBER 3,021,291 2/ 1962 Thlessen 260/29.6 S 3,325,435 6/1967 GlbbS 260/29.6 S

MODIFIED CEMENT COMPOSITIONS HAVING ENHANCED ELASTIC MODULUS Inventors: R. Douglas Eash, Midland; L: F.

Lamoria, Bay City, both of Mich.

Assignee: The Dow Chemical Company,

Midland, Mich.

Filed: Feb. 4, 1972 Appl. No.: 223,741

Related US. Application Data Continuation-in-part of Ser. No. 52,110, July 2, 1970, abandoned.

US. Cl. 260/29.6 S, 94/24, 260/29.6 T, 260/29.6 MM, 260/41 C Int. Cl. C08f 45/24, C08f 45/14 Field of Search 260/29.6 S, 29.7 S, 260/29.6 T

References Cited UNITED STATES PATENTS 4/ I934 Caldwell 260/29.6 S

Primary ExaminerHarold D. Anderson AttorneyWilliam M. Yates et a1.

[5 7] ABSTRACT Normally crystalline vinylidene chloride polymer latex-modified portland cement compositions having exceptionally high elastic modulus by the incorporation therein of from about 1.5 to about 3 percent of composition volume of a fibrous mixture consisting of (a) a nylon fiber and (b) a steel fiber wherein the fibrous materials are present in the mixture in amounts representing a ratio of (a) to (b) of about 1:2 to 2:1 based on mixture volume; which compositions are particularly suited for use in construction in preparing or repairing structures such as pavement and the like requiring high energy absorption properties.

3 Claims, No Drawings NORMALLY CRYSTALLINE VINYLIDENE CHLORIDE POLYMER LATEX AND FIBER MODIFIED CEMENT COMPOSITIONS HAVING ENHANCED ELASTIC MODULUS This application is a continuation-in-part of copending application Ser. No. 52,110 filed July 2, 1970 (now abandoned).

BACKGROUND OF THE INVENTION Normally crystalline vinylidene chloride polymer latex-modified portland cement compositions, are widely used in construction in preparing, patching, resurfacing and repairing various load bearing structures including pavements, airfield runways, bridge floors, floor underlayments, and in areas requiring high energy absorption properties such as developed in explosions and earthquakes and in structures which are subject to impact such as by flying objects. These structural appli cations require a high elastic modulus. The modulus of such compositions is enhanced slightly but insufficiently by the presence of the latex material.

It has also been proposed to add fibrous materials to such latex-modified cement compositions primarily to enhance the tensile strength thereof. However, heretofore, the elastic mdoulus of a given portland cement system has been generally considered to be a constant which does not increase significantly with the addition of fibrous materials. That such is the case is illustrated by the data appearing on Table I of Example I set forth infra.

It has now been discovered, which discovery comprises the present invention, that the elastic modulus of the normally crystalline vinylidene chloride polymer latex-modified cement compositions can be significantly and unexpectedly increased by the addition thereto of the hereinafter specified mixtures of fibrous materials.

SUMMARY OF THE INVENTION The unexpected enhancement in elastic modulus of normally crystalline vinylidene chloride polymer latexmodified portland cement compositions is attained by addition to such cement compositions of from about 1.5 to about 3 percent by composition volume of a fibrous mixture consisting of (a) nylon fiber and (b) steel fiber; wherein the individual fibrous materials are pres ent in such mixture in amounts representing a ratio of (a) to (b) of about 1:2 to 2:1 based on mixture volume.

DESCRIPTION OF THE PREFERRED EMBODIMENTS By the term normally crystalline vinylidene chloride polymer latex as used herein is meant latexes prepared from those polymers of vinylidene chloride which exhibit crystallinity when examined by X-ray diffraction methods or between crossed Nicol prisms and compositions prepared therefrom by the inclusion of modifying agents which compositions retain the working characteristics of the crystalline polymers. The normally crystalline vinylidene chloride polymers are those as described, for example, in the US. Pat. Nos. 2,233,442; 2,251,486; 2,291,670; 2,321,292 and 2,753,321.

Exemplary of such polymers are interpolymers wherein the major polymeric constituent is vinylidene chloride which is present in the latexes in proportions of greater than to about 90 percent by weight being interpolymerized with less than 50 to about 10 percent by weight of at least one interpolymerizable material.

The interpolymerizable material may be composed of at least one monomer having the general formula:

wherein R is hydrogen or the methyl group and X is selected from the group consisting of CN, halogens of atomic numbers 9 to 35, and ester forming groups -COOY, wherein Y is a primary or secondary alkyl group containing up to and including 18 carbon atoms.

Illustrative of monomeric materials applicable in the preparation of suitable interpolymer latexes are methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, sec.-butyl acrylate, tert.-buty1 acrylate, amyl acrylate, isoamyl acrylate, tert.-amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, octyl acrylate, 3,5,5- trimethylhexyl acrylate, decyl acrylate, dodecyl acrylate, octyl acrylate, octadecenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, n-amyl methacrylate, sec.-amyl methacrylate, 2-ethylbutyl methacrylate, octyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, 3,5,5-trimethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, and octadecyl methacrylate and butoxyethyl acrylate or methacrylate or other alkoxyethyl acrylates or methacrylate, vinyl chloride, acrylonitrile, methacrylonitrile, and the like.

Particularly effective latexes are prepared from the interpolymers containing vinylidene chloride, vinyl chloride, and ethyl acrylate in approximate percentage weight proportions of :20:10 and :20:5, respectively; a vinylidene chloride, vinyl chloride and 2- hexylacrylate interpolymer latex the polymeric materials being present in approximate percentage weight proportions of 52:35:13 respectively; and particularly an interpolymer latex containing about 75 parts by weight of vinylidene chloride and about 20 parts by weight vinyl chloride, about 5 parts by weight ethyl acrylate and about 2 parts by weigh of methyl methacrylate. Generally, the latex to cement ratio by weight is preferably between about 0.1 where a neat cement system is used, up to about 0.25, where a conventional aggregate cement system is employed.

The aggregate used may be stone, gravel, concrete, carborundum, aluminum oxide, emery, marble chips, sawdust, cinders, asbestos, mica, talc, flint or manufactured particles such as powdered ceramic material, or any other material which may serve the purpose of sand. The intended end use of the concrete system will serve as a guide to those skilled in the art as to the choice or preferred particle size of the aggregate material to be included in the latex-modified mortar of the present invention.

The fibrous mixtures of the present invention are generally used in amounts of from about 1.5 percent of composition volume, preferably where an aggregate system is used, to about 3 percent of composition volume where a neat cement system is used. Optimum results are obtained wherein the synthetic nylon fiber component of such fibrous mixture and the steel fiber component are present in such mixture in amounts representing a ratio of nylon fiber to steel fiber of about 1:2 to 2:1 based on mixture volume.

The nylon fiber used has an elastic modulus less than the portland cement as well as the steel fibers used. Particularly preferred nylon fibers are those having the necessary elastic modulus and in addition, having a density of about 71 pounds per cubic foot and an elastic modulus of about 3 X 10 psi.

Exemplary of steel fibers which may be used are those fibers having an elastic modulus greater than the nylon fiber and the portland cement used. Particularly preferred steel fibers are those having an elastic modulus of about 29 X 10 psi.

It is to be understood that the size of the nylon or steel fibers may vary within commonly used ranges. Example I In each of a series of individual experiments, the hereinafter identified concrete mixes were prepared and used to make 2 inch by '72 inch by 23 inch flexural bars. Each bar was cured for 24 hours in the molds while covered with wet sponges. The bars were than placed in a 95-100 percent humidity box maintained at a temperature of 75F. Latex-modified bars were cured for 3 days in the humidity box followed by 24 additional days curing at 50 percent relative humidity at 73F. Bars prepared from formulations from which the latex had been excluded were cured for 27 days in a 95-100 percent humidity box maintained at 75F.

After the initial cure, the bars were dried in a 200F oven for 7 days to remove free water in the samples and tested in an Instron testing machine for flexural strength with center point loading over a 10-inch span. The load versus deflection was recorded on a chart on the machine. The elastic modulus of each test bar was calculated over that portion of the curve equal to one third of the ultimate load by the standard formulation.

where E elastic modulus in psi; w load in pounds; L length of test span in inches; s deflection in inches; b width of test bar in inches; d thickness of test bar in inches.

The following Table 1 illustrates the effect of fiber addition on the elastic modulus of nonlatex-modified cement systems wherein each sample was formulated as follows:

Cement Cement System A System B Formulation Ingredient Pounds Pounds Sand 250 (ASTM fine aggregate for concrete passing through a No. 4 screen) Portland Cement 100 100 Water 46 29 Total 396 129 Absolute Volume 2.76 cu. ft. 0.960 cu. ft.

TABLE I Effect of Fiber Addition on Elastic Modulus of Nonlatex Modified Cement Systems Fiber Elastic Modulus Sample No. Type by Vol. (psi)' Cement System A 1 None 2.59 X 10' 2 Nylon 1.75 2.04 X 10' 3 Steel 1.75 2.35 X 10' plus 2.82 X 10' Steel" 1.17 Cement System 8 None 1.58 X 10' 6 Nylon 3 2.03 X 10' 7 Steel 3 0.60 X 10' 8 Nylon 1 plus 1.46 X 10' Steel 2 9 Nylon 2 l plus 2.29 X 10 Steel 1 "Nylon fiber: 15 Denier s4 inch, elastic modulus 3 x 10. 'Steel fiber: Round, low carbon, bright, 1 X 0.016 inch, elastic modu- All of the above values for elastic modulus are within experimental error, except for Sample 7 of Table l. The above data illustrates that the addition of nylon or steel 10 fibers individually or in combination (as prescribed by this invention), does not significantly increase the elastic modulus of the nonlatex-modified cement systems.

The following Table 11 illustrates the effect of latex addition upon the elastic modulus, compression strength and flexural strength of the cement systems of Table I. The latex used was of the following composition:

Formulation Ingredients Parts by Wt.

Vinylidene Chloride 75 Vinyl Chloride 20 Ethyl Acrylate 5 Methyl Methacrylate 2 TABLE I1 Compres- Latex Elastic sion Flexural Sample Solids Modulus Strength Strength No. (lbs.) (psi) (psi) (psi) Cement System A 10 0 2.59x10 7,070 1,550

Cement System The above data illustrate that the addition of the latex to the cement compositions enhances the elastic modulus only slightly while significantly enhancing the compression and flexural strength of the cement system.

The following Table 111 illustrates the effect of fiber addition of the elastic modulus, compression strength and flexural strength of the herein-described latexmodified cement systems, wherein Cement System A (Sample Numbers 14-17 inclusive) contains 20 pounds of latex solids and Cement System B (Sample Numbers 18-22 inclusive) contains 15 pounds of latex solids:

TABLE 111 Compres- Elastic sion Flexural Sample Fiber Modulus Strength Strength No. Type by Vol. (psi) (psi) (Psi) (For comparison) Cement System 14 None 3.16X10 11,900 2,680 15 N IOn" 1.75 3.21 10 11,400 2,800

16 Steel 1.75 3.12 10 12,700 2,700

(The lnvention) 17 Nylon 0.58 s.72 10 11,400 2,230

plus Steel 1.17 Cement System (For Comparison) 18 None 2.|1 10 16,100 2,230 19 Nylon 3 2.22x10' 14,700 3,360 20 Steel 3 2.33x10' 18,100 4,170 (The Invention) 21 Nylon 1 5.58 10' 16,900 3,210

plus Steel 2 22 Nylon 2 405x10 15,100 2,490

plus Steel 1 The above data illustrate the unexpectedly enhanced elastic modulus obtained by the addition of the combination of nylon and steel fibers to the described latexmodified cement system. Such data also illustrate that the enhancement in elastic modulus is obtained without loss in compression or flexural strength.

What is claimed is:

l. A composition comprising essentially of l a normally crystalline vinylidene chloride polymer latexmodified portland cement said normally crystalline vinylidene chloride polymer containing from about 50 to 75 percent by weight vinylidene chloride with the remainder being a monoethylenically unsaturated comonomer selected from the group consisting of vinyl chloride, ethylacrylate, Z-hexylacrylate, methylmethacrylate and mixtures thereof and (2) from about to about 3 percent by composition volume of a fibrous mixture consisting of (a) a fibrous nylon having an elastic modulus of about 3 X 10 psi and (b) a fibrous steel, said fibrous steel having an elastic modulus of about 29 X 10 psi and wherein said fibrous nylon and said fibrous steel are present in amounts representing a ratio of (a) to (b) of about 1:2 to 2:1 based on mixture volume.

2. The composition of claim 1 wherein said fibrous nylon is about 15 denier by 3/4 inch in size and said fibrous steel is about 1 inch in length by 0.016 inch in diameter.

3. The composition of claim 2 wherein said vinylidene chloride polymer is an interpolymer of about parts by weight vinylidene chloride, about 20 parts by weight vinyl chloride, about 5 parts by weight ethylacrylate and about 2 parts by weight methyl methacrylate.

"H050 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,773,700 Dated November 20, 1973 lnventofls) R. Douglas Eash and L2 F. Lamoria It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In Column 3, lines 55-64 in Table I, the following errors have been found.

Inline 64, the numbea w" has been left out from the first column; "Nylon has been left out from the second column and "0.58" has been left out from the third column.

The first part of the table is printed below for easier determination of the errors.

TABLE I Effect of Fiber Addition on Elastic Modulus of Nonlatex Modified Cement Systems Fiber ElasticModulus Sample No. Type by Vol. (psi) Cement System A 1 Y None 2.59x 10 2 Nylon 1.75 I 2 .04,x 1o 3 Steel v 1.75 2.35 -x 1o 4 Nylon 0.58 6

(2) plus 2.82 x l0 Steel l.l7

Signed and sealed this 2nd day of April 1971;,

(SEAL) AtteSt:

EDWARD M.FIETCHER,JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents 

2. The composition of claim 1 wherein said fibrous nylon is about 15 denier by 3/4 inch in size and said fibrous steel is about 1 inch in length by 0.016 inch in diameter.
 3. The composition of claim 2 wherein said vinylidene chloride polymer is an interpolymer of about 75 parts by weight vinylidene chloride, about 20 parts by weight vinyl chloride, about 5 parts by weight ethylacrylate and about 2 parts by weight methyl methacrylate. 